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41.
Recently the hydrogen-bond activated reactions have attracted much attention.1 Takemoto2 reported a highly enantioselective Michael addition of manolate to nitroolefins catalyzed by a bifunctional organocatalyst with tertiary amine and thiourea moiety. As we known,stereoselective conjugate additions of thiols are interesting due to the standpoint of biological and synthetic importance, however, only very limited good results have been obtained except for the works of Shibasaki3, Kanemasa4 and Deng5 et al.In this letter, we report an efficient catalytic asymmetric Michael reactions of thiols to a,a-unsaturated carbonyl compounds promoted by bifunctional organocatalysts. A series of organocatalysts with chiral amine and thiourea structures were designed and synthesized and have been successfully applied in the conjugated additions of thiols to a,a-unsaturated imides and enones.The reactions got quantitative yields and the ee values were up to 84%. It is noteworthy that the a-asymmetric protonation (up to 43% ee) also could be achieved.The Michael addition between aromatic thiols and a,a-unsaturated carbonyl compounds isdescribed as follows:Works to further increase the enantioselectivity is under investigation in our laboratory. 相似文献
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Summary Kinetics of dehydration of equilibrium swollen poly(acrylic acid) hydrogel was investigated using methods of non-isothermal
thermal analysis. Methods of Kissinger, Coats-Redfern, Van Krevelen and Horowitz-Metzger were applied for determination the
kinetics parameters: activation energy (E), pre-exponent (lnA) as well as the kinetics model ƒ(69) for the process of hydrogel dehydration under different heating rates. An existence
of good agreement between determined values of kinetic parameters (Eand A), which were obtained applying different methods under the same heating rate. Functional relationship between changes of
kinetic parameters of dehydration and changes of heating rate was established. An existence of compensation effect is accepted
and explanation of compensation effect appearance during the hydrogel dehydration is suggested. 相似文献
44.
The degradation process of TEOS-PDMS Ormosils containing different amounts of γ -APS has been studied by means of DTA, TG, FTIR and 29Si-NMR measurements. It has been found that the amount of γ -APS improved the thermal properties of Ormosil materials. The increase in γ -APS content causes the increment on the decomposition temperatures and activation energies of the studied Ormosils. These results have been attributed to the favourable effect of γ -APS in the copolymerisation reaction between TEOS and PDMS molecules. 29Si-NMR analyses have shown that the incorporation of γ -APS increases the concentration of D(Q) units in the Ormosil structure, i.e., increases the number of TEOS molecules bonded to PDMS ones. Initial decomposition temperature (IDT), temperature of maximum weight loss rate (Tmax), integral procedure decomposition temperature (IPDT) and activation energy values (E) were calculated from different equations which described the degradation of these materials. Addition of 10 wt% γ -APS produced an increase of 63∘C in the IDT and of 115 and 110∘C, respectively, for Tmax and IPDT (up to 478 and 610∘C) compared to the free γ -APS Ormosil. Activation energy values also rise up to 69.4 kJ⋅ mol−1 by introducing 10 wt% of γ -APS. 相似文献
45.
Omar El Tall Nicole Jaffrezic‐Renault Monique Sigaud Olivier Vittori 《Electroanalysis》2007,19(11):1152-1159
Boron‐doped Diamond (BDD) electrode has become one of the important tools for heavy metal detection. By studying some analytical parameters of DPASV method, like deposition time and potential in different electrolyte concentrations (acetate buffer), the conditions for detecting very low metal ion levels (Zn, Cd, Pb, and Cu) could be chosen. Diluted electrolyte (0.01 M buffer) was one of the factors favoring low detection and quantification limits, but its quantification range is short in comparison to more concentrated media. For ?1.7 V deposition potential, the detection of single metal at ppb levels was reached in 60 s deposition time. Understanding different metal‐metal interactions shows the limits to the simultaneous determination of heavy metals at BDD. Quantification was possible for the simultaneous determination of Zn, Cd and Pb despite the overlapping of Zn and Cd peaks. The performance of the BDD was compared with that of another C‐based solid electrode: the glassy carbon electrode (without mercury plating). A lower base line current, wider potential range, higher sensitivity (3 to 5 times higher than GC) and longevity of the material were noticed for the BDD. 相似文献
46.
CdSe纳米线阵列的制备及其表征(英) 总被引:1,自引:0,他引:1
通过在含有SeSO32-和Cd2+的室温水溶液中,用模板-电沉积法在纳米孔阵列阳极氧化铝膜(AAM)模板中制备了高有序性的CdSe纳米线阵列,并对其形貌、结构和组分进行了表征。扫描电子显微镜(SEM)和透射电子显微镜(TEM)结果表明,纳米线阵列中的CdSe纳米线具有相同的长度和直径,分别对应于使用的AAM模板的厚度和孔径;X-射线衍射(XRD)和X-射线能谱(EDAX)结果表明,CdSe纳米线中Cd和Se的化学组成非常接近于1∶1,其结构为立方CdSe。另外,对模板-电沉积法制备CdSe纳米线的机理进行了讨论。 相似文献
47.
48.
盐酸氨溴索在碳糊电极上阳极伏安法的研究 总被引:4,自引:0,他引:4
在0.5 mol/L H2SO4底液中,用碳糊电极阳极伏安法测定盐酸氨溴索,被测的阳极峰电位为1.10V(vs.SCE),另外,在0.46V处还产生一对可逆的氧化还原峰。1.10 V处的峰电流与盐酸氨溴索的浓度在3.98×10~(-7)~6.34 × 10~(-5)mol/L范围内呈良好的线性关系,该方法的检出下限为3.0 × 10~(-8)mol/L。用标准加入法测得回收率范围为92.8%~102%,RSD为2.9%(n=10)。对电极响应机理进行了初步探讨,氨溴索在1.10 V处的氧化为不可逆过程,其氧化产物在0.460V处产生一对2电子2质子受扩散控制的可逆波,用该波也可进行定量测定并且干扰较少,但灵敏度略低。 相似文献
49.
50.